AM1 study on infra-red spectra of silica clusters modified by fluorine

AM1 molecular orbital (MO) calculations were made for various cluster models of silica and for fluorinated silica. Calculations were made on clusters containing up to 12SiO4 units. On the basis of the relative position and relative intensity of the theoretical vibrational spectra of fluorine-free silica clusters with different sizes and fluorinated silica clusters, the effects of the replacement of OH groups by fluorine on the vibrational spectra of the silica clusters were established. In ring-type silica clusters the absorption around 640–720 cm−1, assignable to the ring vibration within the ring plane, could be seen in the three-membered ring. The intensity of absorption around 500–600 cm−1, assignable to the O–Si–O bending vibration, decreased with increasing size of rings and by the replacement of hydroxyl groups (OH−) by fluorine (F−). In block-type silica clusters all absorption peaks shifted to higher frequencies than those in ring-type silica clusters. The absorption peaks in AM1 calculated vibrational spectra correlated with the experimental IR spectra except for the stretching vibration of Si–F bonds.